The novel hyperbranched poly(trimellitic glyceride) (PTG) starch plasticizer synthesized in our previous study was neutralized with different alkaline metal hydroxides. Mixed with starch, the effects of different alkaline metal cations, M+, on gelatinization of starch suspensions and thermal behaviors of the films were analyzed using RVA and DMA, respectively. The structures of the starch suspensions, films and freeze-dried samples (S/PTG-M) were investigated using DSC, XRD and FTIR spectroscopy, respectively. M+ increased the gelatinization temperature of starch suspensions in the order of S/PTG-Li > S/PTG-Na > S/PTG-K. The formation of a complex between M+ and starch in the films observed using FTIR spectroscopy improved the stability of the starch paste and gel, and increased the gel temperature of starch dispersions. The corresponding starch gel was relatively thermostable, but not shear-resistant. PTG decreased the Tg of starch films with different paired M+. PTG-Li and PTG-K, but not PTG-Na, strengthened the mechanical properties of starch films.